CN104693701A - Low-warpage halogen-free flame-retardant glass fiber reinforced PBT/AS alloy and preparation method thereof - Google Patents
Low-warpage halogen-free flame-retardant glass fiber reinforced PBT/AS alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses low-warpage halogen-free flame-retardant glass fiber reinforced PBT/AS alloy and a preparation method thereof. The alloy is prepared from the following components in percentage by mass: 30-70 percent of polybutylene terephthalate, 15-40 percent of glass fibers, 5-30 percent of styrene-acrylonitrile copolymer, 1-8 parts of a compatilizer, 5-20 percent of a modified hypophosphite flame retardant, 0.1-1 percent of an anti-dripping agent, 0.2-2 percent of an antioxidant and 0.2-1 percent of a lubricant. The alloy has the advantages that the heat resistance and mechanical performance of the material can be remarkably improved by adding the glass fibers, the warpage resistance of the material can be effectively improved by adding a proper amount of AS resin, and the compatibility of glass fibers and a polyester material can be improved by adding the compatilizer. The low-warpage halogen-free flame-retardant glass fiber reinforced PBT/AS alloy has the characteristics of good warpage resistance, excellent size stability, flame retardance, environmental friendliness and excellent mechanical performance.
Description
Technical field
The present invention relates to a kind of material and method of macromolecule modified technical field, specifically a kind of low warpage halogen-free flame-retardant glass fiber strengthens PBT/AS Alloy And Preparation Method.
Background technology
Polybutylene terephthalate (PBT) is one of several engineering plastics that application is maximum at present, he has good molding processibility, crystallization velocity is fast, product surface good luster, chemicals-resistant and oil-proofness excellent, particularly arc resistance is excellent, and less than Other Engineering plastics, these Comprehensive Characteristics make it be widely used in the industries such as electric and electronic automobile mechanical instrument and do structural part.
Pure PBT resin mechanical property is general, the shortcomings such as the heat-drawn wire under load is lower, and flame retardant properties is not good.Improve the effectively the most universal method that the comprehensive physical mechanics property the subject of knowledge and the object of knowledge of PBT material uses, adopt glass fiber reinforcement exactly, can significantly improve its physical strength and heat-drawn wire like this.And major part adopts glass fiber reinforcement or inorganic fill modification, but goods vertical, horizontal shrinking percentage is inconsistent after glass fiber reinforcement, easily there is buckling deformation during injection moulding large goods, affect use and the outward appearance of product, also have the shortcoming such as poor toughness, poor dimensional stability of material.
At present, the flame-retardant system being applicable to PBT comprises containing halogen and the large system of Halogen two.Due to halogen containing flame-retardant, the amount of being fuming is large in combustion, and discharges poisonous, corrosive gas, contaminate environment, health risk, and halogen-free flame retardants has good flame retardation effect; Polluting the features such as little, is technological difficulties and the focus of existing research.Halogen system comprises: inorganic fire-retarded system, Intumescent Retardant System, silicon system, phosphorus flame retardant.Inorganic combustion inhibitor have nontoxic, press down cigarette, the advantage such as cheap, but the flame retarding efficiency of inorganic powdered filler is lower, proportion is comparatively large, can obvious deteriorated PBT processing characteristics, mechanical property, outward appearance and electrical property with poor, a large amount of interpolation of matrix phase capacitive.Intumescent Retardant System, wherein with ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide for representative, have nontoxic, press down the advantage such as cigarette, but there is exudative and water miscible problem in tetramethylolmethane, and Intumescent Retardant System is incompatible with polymkeric substance, mechanical property and the water tolerance of polymkeric substance also can be reduced, so Intumescent Retardant System is also restricted in the application of PBT after adding.Silicon-series five-retardant (polysiloxane copolymer, organo-siloxane, phenmethyl silicone, with silicone resin etc.), have efficient, low toxicity, pollution-free, be fuming few, the also less and attention to the damage of the mechanical property of resin, but silicon-series five-retardant is expensive, is only applicable to special dimension and uses.
Hypophosphorous acid metal salt, if calcium propionate is very effective halogen-free flame retardants, when with nitrogenated flame retardant, as melamine cyanurate, the composite polyester composite field that is used in such as melamine phosphate can obtain satisfied flame retardant effect, simultaneously less on the resistance toheat impact of material.But when hypophosphorous acid metal salt is directly used in flame-retardant PBT, strong hydrolytic action can be there is and cause polyester significantly to degrade, causing product surface to there is a large amount of filamentary silvers, the bad phenomenon such as foaming.
Based on above all analyses, prepare the main difficult point of fiber glass reinforced PBT material at present and hot technology is to prepare a kind of good mechanical property, flame-proof environmental protection is effective, the material that resistance to warpage is good.
Through finding the retrieval of prior art, Chinese patent literature CN102372907A, CN102649870ACN102875985A, CN103289328A and CN103525018A have prepared multiple halogen-free flame-retardant glass fiber by different methods and have strengthened resin, and improve the mechanical property of glass fiber reinforced PBT resin.Although above patent solves halogen-free flameproof problem, the dimensional stability warpage issues of solution material of having no idea.
Open (bulletin) the day 2012.07.11 of Chinese patent literature CN102558699A, discloses a kind of fiberglass reinforced fire retardant AS/PBT material and preparation method thereof, belongs to polymer processing field.By weight percentage, its component and content are: styrene-acrylonitrile copolymer 25 ~ 65, polybutylene terephthalate 5 ~ 25, glass fibre 10 ~ 30, bromide fire retardant 5 ~ 20, Sb system fire retardant 2 ~ 15, antidrip additive 0.1 ~ 1.4, oxidation inhibitor 0.3 ~ 1, compatilizer 3-10.Compared with prior art, described patent is AS is that master has halogen flame-retardant system alloy to described patent, and this patent is the Zero halogen flame resistance alloy based on PBT, so do not have conflicting from formula, performance and use.
Open (bulletin) the day 2012.12.16 of Chinese patent literature CN102838853A, disclose a kind of resistance to warpage fiberglass reinforced fire retardant PBT material and preparation method thereof, described material is made up of the raw material of following weight part: PBT resin 40 ~ 70 parts, 10 ~ 50 parts, glass fibre, mica powder 3 ~ 10 parts, brominated epoxy resin 5 ~ 15 parts, antimonous oxide 1 ~ 5 part, 0.2 ~ 1.5 part, oxidation inhibitor; Take PBT resin, mica powder, brominated epoxy resin, antimonous oxide and oxidation inhibitor by weight ratio, put into high-speed mixer for dry mixing; Above-mentioned blend is dropped into twin screw extruder through melt extruding, granulation, wherein glass fibre is added by the glass fiber opening of machine, and interpolation speed is controlled by screw speed; The particle produced is toasted, obtains resistance to warpage fiberglass reinforced fire retardant PBT material.Although described patent solves warpage issues, but still adopt be halogen-free flame retardants and have the composite of halogen auxiliary agent, so still certain environmental issue can be produced when using in the material, and material kind uses mica can increase the surface gloss of material, can cause eye strain in the use procedure of automobile dulling material.
The technology that above patent provides solves halogen-free flameproof problem or warpage issues from different angles.But do not solve the problem of these two aspects simultaneously.This technological invention is exactly for the deficiencies in the prior art, provides a kind of and overcomes the warpage issues of fiber glass reinforced PBT material and the preparation method of halogen-free flameproof problem simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is warpage issues and the halogen-free flameproof problem of PBT.Overcome traditional fiberglass reinforcing PBT alloy material warpage serious, the defect that dimensional stability is poor and shock strength is not high, provides a kind of shock strength high, the environment friendly halogen-free fireproof fiberglass reinforcing PBT alloy material of good stability of the dimension and low warpage.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of low warpage halogen-free flame-retardant glass fiber and strengthen PBT/AS alloy material, comprise each component of following mass percent:
Preferably, described glass fibre is the mixture of one or more in alkali free glass fibre, medium-alkali glass fibre, high-strength glass fibre, short glass fiber, and fiber filament diameter is 5 ~ 20 μm.
Preferably, described styrene-acrylonitrile copolymer melt index >=2g/10min under 200 DEG C × 5kg test condition.
Preferably, described compatilizer is at least one in styrene-acrylonitrile-glycidyl methacrylate copolymer (SAG-001), styrene-maleic anhydride copolymer (SMA), styrene-acrylonitrile-copolymer-maleic anhydride (SAMAH), ethylene-ethylacrylate-glycidyl methacrylate copolymer (AX8900), Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer (PTW), Polyolefin Grafted Maleic Anhydride.
Preferably, described modification hypophosphite fire retardant is Clariant ExolitOP1240.
Preferably, described anti-dripping agent comprises the tetrafluoroethylene (PTFE) that molecular weight is 3,000,000 ~ 5,000,000.
Preferably, described oxidation inhibitor comprises as main anti-Hinered phenols material with as auxiliary anti-phosphorous acid esters material; Described Hinered phenols material comprises 2,6-, tri-grades of butyl-4-methylphenols, two (3,5-, tri-grades of butyl-4-hydroxy phenyls) thioether, four (β-(3,5-, tri-grades of butyl-4-hydroxy phenyls) propionic acid) pentaerythritol ester etc.; Described phosphorous acid esters material is as three [2.4-di-tert-butyl-phenyl] phosphorous acid ester etc.
Preferably, the mass ratio of described Hinered phenols material and phosphorous acid esters material is 1:1.
Preferably, described lubricant is lipid acid, soap or fatty acid acyl amine material; Described lipid acid is as stearic acid, pentaerythritol tetrastearate etc.; Described soap is as calcium stearate, sodium stearate, Magnesium Stearate, Zinic stearas etc.; Described fatty acid acyl amine material is as ethylene bis stearic acid amide etc.
More preferably, described lubricant is pentaerythritol tetrastearate, and mass percent is 0.2 ~ 1%, and too high addition can cause matrix resin to plastify near bad and cast gate and occur demixing phenomenon.
Second aspect, the present invention relates to the preparation method that a kind of low warpage halogen-free flame-retardant glass fiber strengthens PBT/AS alloy material, polybutylene terephthalate (PBT), styrene-acrylonitrile copolymer, compatilizer, modification hypophosphite fire retardant, anti-dripping agent, oxidation inhibitor, lubricant are mixed in mass ratio, adds to twin screw extruder; Glass fibre is added by the glass fiber opening of twin screw extruder, melting; Extruding pelletization, dry, obtain low warpage halogen-free flame-retardant glass fiber and strengthen PBT/AS alloy material.
Preferably, described twin screw extruder processing parameter is: district's temperature: 200 ~ 210 DEG C; Two district's temperature: 210 ~ 220 DEG C; Three district's temperature: 220 ~ 240 DEG C; Four district's temperature: 220 ~ 240 DEG C; Five district's temperature: 220 ~ 240 DEG C; Six district's temperature: 220 ~ 240 DEG C; Seven district's temperature: 220 ~ 240 DEG C; Eight district's temperature: 220 ~ 240 DEG C; Nine district's temperature: 220 ~ 240 DEG C; Screw speed is 200 ~ 400r/min.
Preferably, described mixing adopts moderate-speed mixers.
Compared with prior art, the present invention has following beneficial effect:
(1) the low warpage halogen-free flame-retardant glass fiber of one provided by the invention strengthens PBT/AS alloy material, comprise PBT resin, glass fibre, styrene-acrylonitrile copolymer, compatilizer, modification hypophosphite fire retardant, other processing aid, add resistance toheat and mechanical property that glass fibre can improve material significantly;
(2) resistance to warping that appropriate AS resin effectively can improve material is added, compatilizer can improve the consistency of glass and polyester material, particularly SAG-001 adds the overall compatibility of AS resin and PBT and glass, the that resist warping of low warpage halogen-free flame-retardant glass fiber enhancing PBT/AS alloy material prepared by the present invention is effective, dimensional stability good, flame-proof environmental protection, good mechanical performance.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
comparative example 1
Raw materials used and the mass percent of this comparative example is: polybutylene terephthalate 69%, glass fibre 30%, anti-dripping agent SN33000.4%, antioxidant 1010 0.2%, irgasfos 168 0.2%, lubricant (pentaerythritol tetrastearate) 0.2%.
The preparation method of the present embodiment was specific as follows: by PBT resin at 120 DEG C dry 4 hours, after by above-mentioned blend composition stirrer for mixing evenly after add in twin screw extruder, add in the 4th humidity province of twin screw extruder the glass fibre that weight percentage is 30%, twin screw extruder processing parameter is as follows: district's temperature: 200 ~ 210 DEG C; Two district's temperature: 210 ~ 220 DEG C; Three district's temperature: 220 ~ 240 DEG C; Four district's temperature: 220 ~ 240 DEG C; Five district's temperature: 220 ~ 240 DEG C; Six district's temperature: 220 ~ 240 DEG C; Seven district's temperature: 220 ~ 240 DEG C; Eight district's temperature: 220 ~ 240 DEG C; Nine district's temperature: 220 ~ 240 DEG C; Screw speed is 350r/min.By the particle that becomes as stated above in the baking oven of 100 DEG C dry 3 hours, then dried particle is carried out injection moulding preparation standard test bars on injection moulding machine, and the mechanical property of test bars, warpage and flame retardant properties.Injection temperature: before, during and after, nozzle is followed successively by 240 ~ 250 DEG C, 240 ~ 250 DEG C, 240 ~ 250 DEG C, 240 ~ 250 DEG C.Test result is in table 1.
embodiment 1
Raw materials used and the mass percent of the present embodiment is: polybutylene terephthalate 55%, glass fibre (alkali-free, fiber filament diameter is 20 μm) 25%, styrene-acrylonitrile copolymer 5%, SAG-0012% modification hypophosphite fire retardant 12%, anti-dripping agent SN33000.4%, antioxidant 1010 0.2%, irgasfos 168 0.2%, lubricant (pentaerythritol tetrastearate) 0.2%.
The preparation method of the present embodiment was specific as follows: by PBT resin at 120 DEG C dry 4 hours, after by above-mentioned blend composition stirrer for mixing evenly after add in twin screw extruder, the glass fibre that weight percentage is 25% is added in the 4th humidity province of twin screw extruder, the particle produced in the baking oven of 100 DEG C dry 3 hours, then dried particle is carried out injection moulding preparation standard test bars on injection moulding machine, and the mechanical property of test bars, warpage and flame retardant properties.Twin screw extruder processing parameter and dry injection parameters operate identical with comparative example.
embodiment 2
Raw materials used and the mass percent of the present embodiment is: polybutylene terephthalate 45%, glass fibre (high-strength, spacing filament diameter 5 μm) 25%, styrene-acrylonitrile copolymer 15%, SAG-0012%, modification hypophosphite fire retardant 12%, anti-dripping agent SN33000.4%, antioxidant 1010 0.2%, irgasfos 168 0.2%, lubricant (pentaerythritol tetrastearate) 0.2%.
The preparation method of the present embodiment was specific as follows: by PBT resin at 120 DEG C dry 4 hours, after by above-mentioned blend composition stirrer for mixing evenly after add in twin screw extruder, the glass fibre that weight percentage is 25% is added in the 4th humidity province of twin screw extruder, the particle produced in the baking oven of 100 DEG C dry 3 hours, then dried particle is carried out injection moulding preparation standard test bars on injection moulding machine, and the mechanical property of test bars, warpage and flame retardant properties.Twin screw extruder processing parameter and dry injection parameters operate identical with comparative example.
embodiment 3
Raw materials used and the mass percent of the present embodiment is: polybutylene terephthalate 35%, glass fibre (short glass fiber) 30%, styrene-acrylonitrile copolymer 20%, SAG-0012%, modification hypophosphite fire retardant 12%, anti-dripping agent SN33000.4%, antioxidant 1010 0.2%, irgasfos 168 0.2%, lubricant (pentaerythritol tetrastearate) 0.2%.
The preparation method of the present embodiment was specific as follows: by PBT resin at 120 DEG C dry 4 hours, after by above-mentioned blend composition stirrer for mixing evenly after add in twin screw extruder, the glass fibre that weight percentage is 30% is added in the 4th humidity province of twin screw extruder, the particle produced in the baking oven of 100 DEG C dry 3 hours, then dried particle is carried out injection moulding preparation standard test bars on injection moulding machine, and the mechanical property of test bars, warpage and flame retardant properties.Twin screw extruder processing parameter and dry injection parameters operate identical with comparative example.
embodiment 4
Raw materials used and the mass percent of the present embodiment is: polybutylene terephthalate 45%, glass fibre 25%, styrene-acrylonitrile copolymer 15%, AX89002%, modification hypophosphite fire retardant 12%, anti-dripping agent SN33000.4%, antioxidant 1010 0.2%, irgasfos 168 0.2%, lubricant (pentaerythritol tetrastearate) 0.2%.
The preparation method of the present embodiment was specific as follows: by PBT resin at 120 DEG C dry 4 hours, after by above-mentioned blend composition stirrer for mixing evenly after add in twin screw extruder, the glass fibre that weight percentage is 25% is added in the 4th humidity province of twin screw extruder, the particle produced in the baking oven of 100 DEG C dry 3 hours, then dried particle is carried out injection moulding preparation standard test bars on injection moulding machine, and the mechanical property of test bars, warpage and flame retardant properties.Twin screw extruder processing parameter and dry injection parameters operate identical with comparative example.
embodiment 5
Raw materials used and the mass percent of the present embodiment is: polybutylene terephthalate 45%, glass fibre 25%, styrene-acrylonitrile copolymer 15%, PTW 2%, modification hypophosphite fire retardant 12%, anti-dripping agent SN33000.4%, antioxidant 1010 0.2%, irgasfos 168 0.2%, lubricant (pentaerythritol tetrastearate) 0.2%.
The preparation method of the present embodiment was specific as follows: by PBT resin at 120 DEG C dry 4 hours, after by above-mentioned blend composition stirrer for mixing evenly after add in twin screw extruder, the glass fibre that weight percentage is 25% is added in the 4th humidity province of twin screw extruder, the particle produced in the baking oven of 100 DEG C dry 3 hours, then dried particle is carried out injection moulding preparation standard test bars on injection moulding machine, and the mechanical property of test bars, warpage and flame retardant properties.Twin screw extruder processing parameter and dry injection parameters operate identical with comparative example.
embodiment 6 ~ 9
Constituent species and the preparation method of alloy involved by embodiment 6 ~ 9 are identical with embodiment 1, and change part is only the component concentration be described in table 1 below:
The content of table 1 alloy involved by embodiment 6 ~ 9
performance evaluation mode and the standard of implementation
Tensile property test is undertaken by ASTM D638, and specimen size is 165*13*3.2, and draw speed is 50mm/min;
Bending property test is undertaken by ASTM D790, and specimen size is 63.5*12.7*3.2, and span is 50mm, and speed is 3mm/min;
Chalpy impact test is undertaken by ASTM D256, and specimen size is 63.5*12.7*3.2, and residue width is 10.15;
Buckling deformations amount is pressed ASTM D955 and is tested molding shrinkage standard testing;
Flame retardant test according to international UL94 standard testing, batten 120*12.7*1.6mm.
The comprehensive mechanical property of material is evaluated by the test tensile strength of gained and the numerical value of flexural strength; That resist warping effect is evaluated according to deformation quantity.
The mechanical and physical performance of fiberglass reinforced fire retardant PBT/AS alloy material prepared by this comparative example 1 and embodiment 1 ~ 5 is as shown in table 2:
Table 2
The comprehensive mechanical property of embodiment 1 ~ 5 is excellent as can be seen from Table 2, and molding shrinkage is much little compared to comparative example 1, and dimensional stability is good, and halogen-free flameproof performance is excellent.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. low warpage halogen-free flame-retardant glass fiber strengthens a PBT/AS alloy material, it is characterized in that, comprises each component of following mass percent:
2. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, it is characterized in that, described glass fibre is one in alkali free glass fibre, medium-alkali glass fibre, high-strength glass fibre, short glass fiber or mixture, and fiber filament diameter is 5 ~ 20 μm.
3. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, and it is characterized in that, described styrene-acrylonitrile copolymer is melt index >=2g/10min under 200 DEG C × 5kg test condition.
4. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, it is characterized in that, described compatilizer is at least one in styrene-acrylonitrile-glycidyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-copolymer-maleic anhydride, ethylene-ethylacrylate-glycidyl methacrylate copolymer, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer, Polyolefin Grafted Maleic Anhydride.
5. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, and it is characterized in that, described modification hypophosphite fire retardant is Clariant ExolitOP1240.
6. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, and it is characterized in that, described anti-dripping agent comprises the tetrafluoroethylene that molecular weight is 3,000,000 ~ 5,000,000.
7. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, it is characterized in that, described oxidation inhibitor comprises as main anti-Hinered phenols material with as auxiliary anti-phosphorous acid esters material; Described is 1:1 as main anti-Hinered phenols material and the mass ratio as auxiliary anti-phosphorous acid esters material.
8. low warpage halogen-free flame-retardant glass fiber according to claim 1 strengthens PBT/AS alloy material, and it is characterized in that, described lubricant is lipid acid, soap or fatty acid acyl amine material.
9. the preparation method of a low warpage halogen-free flame-retardant glass fiber enhancing PBT/AS alloy material according to claim 1, it is characterized in that, polybutylene terephthalate, styrene-acrylonitrile copolymer, compatilizer, modification hypophosphite fire retardant, anti-dripping agent, oxidation inhibitor, lubricant are mixed in mass ratio, adds to twin screw extruder; Glass fibre is added by the glass fiber opening of twin screw extruder, melting; Extruding pelletization, dry, obtain low warpage halogen-free flame-retardant glass fiber and strengthen PBT/AS alloy material.
10. low warpage halogen-free flame-retardant glass fiber according to claim 9 strengthens the preparation method of PBT/AS alloy material, and it is characterized in that, described twin screw extruder processing parameter is: district's temperature: 200 ~ 210 DEG C; Two district's temperature: 210 ~ 220 DEG C; Three district's temperature: 220 ~ 240 DEG C; Four district's temperature: 220 ~ 240 DEG C; Five district's temperature: 220 ~ 240 DEG C; Six district's temperature: 220 ~ 240 DEG C; Seven district's temperature: 220 ~ 240 DEG C; Eight district's temperature: 220 ~ 240 DEG C; Nine district's temperature: 220 ~ 240 DEG C; Screw speed is 200 ~ 400r/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419252A (en) * | 2015-11-19 | 2016-03-23 | 东莞市众一新材料科技有限公司 | PBT composite with low warping and high surface glossiness and preparation method thereof |
| CN107057299A (en) * | 2017-04-18 | 2017-08-18 | 广东圆融新材料有限公司 | A kind of halogen free flame-retardant reinforced PBT composite material and its preparation method and application |
| CN110862655A (en) * | 2019-12-11 | 2020-03-06 | 宁波华腾首研新材料有限公司 | PBT/SAN composite material and preparation method and application thereof |
| CN111621123A (en) * | 2020-05-11 | 2020-09-04 | 天津金发新材料有限公司 | Low-warpage PET/PBT composite material and preparation method thereof |
| CN112724501A (en) * | 2020-12-28 | 2021-04-30 | 会通新材料股份有限公司 | Toughened composite, PBT composite material and preparation method thereof |
| CN113337089A (en) * | 2021-07-22 | 2021-09-03 | 合肥圆融新材料有限公司 | Glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0912849A (en) * | 1995-06-29 | 1997-01-14 | Matsushita Electric Works Ltd | Pbt resin molding material and its molded item |
| CN101747602A (en) * | 2008-12-18 | 2010-06-23 | 第一毛织株式会社 | Glass fiber-reinforced polyester resin composition and molded product using the same |
| CN102070885A (en) * | 2010-12-15 | 2011-05-25 | 深圳市富恒塑胶新材料有限公司 | Halogen-free flame-retardant glass fiber reinforced polyester terephthalate (PET)/poly butylenes terephthalate (PBT) alloy and preparation method thereof |
| CN102746624A (en) * | 2012-07-24 | 2012-10-24 | 北京市化学工业研究院 | Preparation method for flame-retardant polybutylene terephthalate engineering plastic |
| CN103450642A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon-fiber-reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
-
2015
- 2015-02-26 CN CN201510089134.XA patent/CN104693701A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0912849A (en) * | 1995-06-29 | 1997-01-14 | Matsushita Electric Works Ltd | Pbt resin molding material and its molded item |
| CN101747602A (en) * | 2008-12-18 | 2010-06-23 | 第一毛织株式会社 | Glass fiber-reinforced polyester resin composition and molded product using the same |
| CN102070885A (en) * | 2010-12-15 | 2011-05-25 | 深圳市富恒塑胶新材料有限公司 | Halogen-free flame-retardant glass fiber reinforced polyester terephthalate (PET)/poly butylenes terephthalate (PBT) alloy and preparation method thereof |
| CN102746624A (en) * | 2012-07-24 | 2012-10-24 | 北京市化学工业研究院 | Preparation method for flame-retardant polybutylene terephthalate engineering plastic |
| CN103450642A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon-fiber-reinforced halogen-free flame-retardant PBT (polybutylene terephthalate) composite material and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419252A (en) * | 2015-11-19 | 2016-03-23 | 东莞市众一新材料科技有限公司 | PBT composite with low warping and high surface glossiness and preparation method thereof |
| CN107057299A (en) * | 2017-04-18 | 2017-08-18 | 广东圆融新材料有限公司 | A kind of halogen free flame-retardant reinforced PBT composite material and its preparation method and application |
| CN107057299B (en) * | 2017-04-18 | 2019-05-24 | 广东圆融新材料有限公司 | A kind of halogen free flame-retardant reinforced PBT composite material and its preparation method and application |
| CN110862655A (en) * | 2019-12-11 | 2020-03-06 | 宁波华腾首研新材料有限公司 | PBT/SAN composite material and preparation method and application thereof |
| CN110862655B (en) * | 2019-12-11 | 2021-09-24 | 宁波华腾首研新材料有限公司 | PBT/SAN composite material and preparation method and application thereof |
| CN111621123A (en) * | 2020-05-11 | 2020-09-04 | 天津金发新材料有限公司 | Low-warpage PET/PBT composite material and preparation method thereof |
| CN112724501A (en) * | 2020-12-28 | 2021-04-30 | 会通新材料股份有限公司 | Toughened composite, PBT composite material and preparation method thereof |
| CN112724501B (en) * | 2020-12-28 | 2022-03-22 | 会通新材料股份有限公司 | Toughened composite, PBT composite material and preparation method thereof |
| CN113337089A (en) * | 2021-07-22 | 2021-09-03 | 合肥圆融新材料有限公司 | Glass fiber reinforced PBT (polybutylene terephthalate) composite material and preparation method thereof |
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Application publication date: 20150610 |